Chain modification of gaseous methane using aqueous electrochemical activation at a three-phase interface

ABSTRACT

In a first aspect, a method for chain modification of hydrocarbons and organic compounds comprises: contacting an aqueous electrolyte, a powered electrode including a catalyst, and a gaseous methane feedstock in a reaction area; and activating the methane in an aqueous electrochemical reaction to generate methyl radicals at the powered electrode and yield a Song chained hydrocarbon. In a second aspect, method for chain modification of hydrocarbons and organic compounds comprises: contacting an aqueous electrolyte with a catalyst in a reaction area; introducing a gaseous methane feedstock directly into the reaction area under pressure; and reacting the aqueous electrolyte, the catalyst, and the gaseous methane feedstock at temperatures in the range of −10 C to 1000 C and at pressures in the range of 0.1 ATM to 100 ATM.

The priority of U.S. Application Ser. No. 61/608,583, entitled, “AnElectrochemical Process for Direct one step conversion of methane toEthylene on a Three Phase Gas, Liquid, Solid Interface”, and filed Mar.8, 2012, in the name of the inventor Ed Chen is hereby claimed pursuantto 35 U.S.C. §119(e). This application is commonly assigned herewith andis also hereby incorporated for all purposes as if set forth verbatimherein.

The priority of U.S. Application Ser. No. 61/713,487, entitled, “AProcess for Electrochemical Fischer Trospch”, filed Oct. 13, 2012, inthe name of the inventor Ed Chen is hereby claimed pursuant to 35 U.S.C.§119(e). This application is commonly assigned herewith and is alsohereby incorporated for all purposes as if set forth verbatim herein.

CROSS-REFERENCE TO RELATED APPLICATIONS

Not applicable.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

BACKGROUND

This section of this document introduces information about and/or fromthe art that may provide context for or be related to the subject matterdescribed herein and/or claimed below. It provides backgroundinformation to facilitate a better understanding of the various aspectsof the claimed subject matter. This is therefore a discussion of“related” art. That such art is related in no way implies that it isalso “prior” art. The related art may or may not be prior art. Thediscussion in this section of this document is to be read in this light,and not as admissions of prior art.

Prior art commercial processes for converting methane to otherhydrocarbons, for example; sometimes include a partial oxidation processthat is highly energy intensive and operates under high pressures andtemperatures. The actual syngas cleanup step occurs after the syngas hasbeen cooled. Tar, oils, phenols, ammonia and water co-products arecondensed from the gas stream and purified and sent on. The gas moves toa cleaning area where further impurities are removed and finally carbondioxide is removed. The syngas is then passed under high pressures (30bars) with some more recent “low pressure” processes operating atslightly above 10 bars at approximately 200-400 degrees Celsius to formhydrocarbons, oxygenates, and other carbon and hydrogen based species.The high pressure reactions utilize iron or nickel as their catalysts,while low pressure synthesis often uses cobalt. These processes usesolid electrolytes rather than aqueous electrolytes.

Another problem with methane activation is catalyst deactivation andregeneration, temperature control, and high pressures. Catalysts areoften deactivated when the surface is covered by waxes and coke (carbonblack). The high temperatures also produce undesirable products such aswax which tends to deactivate the catalyst. Finally, water is also abyproduct of this reaction.

The art therefore possesses a number of methane activation processesthat, even if satisfactory in some respects, have several drawbacks. Theart furthermore is always receptive to improvements or alternativemeans, methods and configurations. Therefore the art will well receivethe technique described herein.

SUMMARY

In a first aspect, a method for chain modification of hydrocarbons andorganic compounds comprises: contacting an aqueous electrolyte, apowered electrode including a catalyst, and a gaseous methane feedstockin a reaction area; and activating the methane in an aqueouselectrochemical reaction to generate methyl radicals at the poweredelectrode and yield a long chained hydrocarbon.

In a second aspect, method for chain modification of hydrocarbons andorganic compounds comprises: contacting an aqueous electrolyte with acatalyst in a reaction area; introducing a gaseous methane feedstockdirectly into the reaction area under pressure; and reacting the aqueouselectrolyte, the catalyst, and the gaseous methane feedstock attemperatures in the range of −10 C to 900 C and at pressures in therange of 0.1 ATM to 100 ATM.

The above presents a simplified summary of the presently disclosedsubject matter m order to provide a basic understanding of some aspectsthereof. The summary is not an exhaustive overview, nor is it intendedto identify key or critical elements to delineate the scope of thesubject matter claimed below. Its sole purpose is to present someconcepts in a simplified form as a prelude to the more detaileddescription set forth below.

BRIEF DESCRIPTION OF THE DRAWINGS

The claimed subject matter may be better understood by reference to thefollowing description taken in conjunction with the accompanyingdrawings, in which like reference numerals identify like elements and inwhich;

FIG. 1 depicts one particular embodiment of an electrolytic cell inaccordance with some aspects of the presently disclosed technique.

FIG. 2 graphically illustrates one particular embodiment of a process inaccordance with other aspects of the presently disclosed technique.

FIG. 3A-FIG. 3B depict a copper mesh reaction electrode as may be usedin some embodiments.

FIG. 4A-FIG. 4B depict a gas diffusion electrode as may be used in someembodiments.

FIG. 5A-FIG.-5B depicts a gas diffusion electrode as may be used in someembodiments.

FIG. 6 depicts a portion of an embodiment in which the electrodes areelectrically short circuited.

While the invention is susceptible to various modifications andalternative forms, the drawings illustrate specific embodiments hereindescribed in detail by way of example. It should be understood, however,that the description herein of specific embodiments is not intended tolimit the invention to the particular forms disclosed, but on thecontrary, the intention is to cover all modifications, equivalents, andalternatives falling within the spirit and scope of the invention asdefined by the appended claims.

DETAILED DESCRIPTION

Illustrative embodiments of the subject matter claimed below will now bedisclosed. In the interest of clarity, not all features of an actualimplementation are described in this specification. It will beappreciated that in the development of any such actual embodiment,numerous implementation-specific decisions must be made to achieve thedevelopers' specific goals, such as compliance with system-related andbusiness-related constraints, which will vary from one implementation toanother. Moreover, it will be appreciated that such a developmenteffort, even if complex and time-consuming, would be a routineundertaking tor those of ordinary skill in the art having the benefit ofthis disclosure.

The presently disclosed technique is a process for converting gaseoushydrocarbons to longer chained liquid hydrocarbons, longer chainedgaseous hydrocarbons, branched-chain liquid hydrocarbons, branched-chaingaseous hydrocarbons, as well as chained and branched-chain organiccompounds. In general, the method is for chain modification ofhydrocarbons and organic compounds, including chain lengthening. Thisprocess more particularly uses aqueous electrolytes to act as a reducingatmosphere and hydrogen and oxygen source for hydrocarbon gases. Theprocess in the disclosed technique is Aqueous Electrochemical Activationof Methane (AEAM) on three phase interface of gas-liquid-solidelectrode. AEAM directly turns natural gas and other sources of methane(CH₄) into C₂+ hydrocarbons and other organic compounds. One exemplaryproduct is ethylene (C₂H₄) and alcohols such as methanol, ethanol,propanol, and/or butanol.

The reaction of hydrocarbon gases may be successfully achieved with anaqueous electrochemical solution serving as a liquid ion source alongwith the supply for hydrogen or singlet oxygen being provided by theaqueous electrolyte through acids and/or bases of the aqueouselectrolyte. The gaseous hydrocarbon is balanced with the aqueouselectrolyte at a solid phase thin film catalyst which is connected tothe reaction electrode of an electrolytic cell. The reaction may also beadjusted with different pHs or any kind of additive in the electrolyticsolution.

The reaction works by utilizing a 3 phase interface which defines areaction area. A catalyst, a liquid, and a gas a positioned in the samelocation and an electric potential is applied to make electronsavailable to the reaction site. When methane is used as the gas it ispossible to create methane radicals which then join with other moleculesor parts of molecules or themselves to create longer chainedhydrocarbons and/or organic molecules. The reaction site can also causebranched chain production by reacting with a newly created molecule andbuilding on that or continuous chain building. Thus from the simplemolecule of methane, CH4, chains of molecules can be built. Existingchained molecules can be lengthened, and existing chained molecules canbe branched. A simple example is methane (CH₄) can be converted tomethanol, CH₃(OH). Different voltages create different reaction productdistributions or facilitate different reaction types.

This aqueous electrochemical reaction includes a reaction that proceedsat room temperature and pressure, although higher temperatures andpressures may be used. In general, temperatures may range from −10C to240C, or from −10C to 1000C, and pressures may range from 0.1 ATM to 10ATM, or from 0.1 ATM to 100 ATM. The process generates reactive methylradicals through the reaction on the reaction electrodes. On thereaction electrode, the production of methyl radicals occurs.

In at least some embodiments, the reactants need no pre-treatment.Typically methanol from methane must first go through steam reforming toproduce syngas (CO and H₂). The presently disclosed technique canperform the production of methanol without reforming to produce syngas.Similarly, as described further below, the gaseous methane feedstock maybe introduced “directly” into the chamber of an electrochemical cell.

In general, the method introduces a liquid ion source into a firstchamber into contact with a catalyst supporting reaction electrode whilea counter electrode is disposed in the liquid ion source. The reactionelectrode is powered. A gaseous methane feedstock is then introduceddirectly into a second chamber under enough pressure to overcome thegravitational pressure of the column of electrolyte, which depends onthe height of the water, to induce a reaction among the liquid ionsource, the catalyst, and the gaseous methane feedstock when theelectrodes are powered.

In the embodiments illustrated herein, the technique employs anelectrochemical ceil such as the one illustrated in FIG. 1. Theelectrochemical cell 100 generally comprises a reactor 105 in onechamber 110 of which are positioned two electrodes 115, 116, a cathodeand an anode, separated by a liquid ion source, i.e., an electrolyte120. Those in the art will appreciate that the identity of theelectrodes 115, 116 as cathode and anode is a matter of polarity thatcan vary by implementation. In the illustrated embodiment, the counterelectrode 115 is the anode and the reaction electrode 116 is thecathode. The reaction electrode 116 shall be referred to as the“reaction” electrode and the counter electrode 115 the “counter”electrode for reasons discussed further below.

There is also a second chamber 125 into which a gaseous methanefeedstock 130 is introduced as described below. The two chambers arejoined by apertures 135 through the wall 140 separating the two chambers110, 125. The reactor 105 may be constructed in conventional fashionexcept as noted herein. For example, materials selection, fabricationtechniques, and assembly processes in light of the operationalparameters disclosed herein will be readily ascertainable to thoseskilled in the art.

Catalysts will be implementation specific depending, at least in part,on the implementation of the reaction electrode 116. Depending on theembodiment, suitable catalysts may include, but are not limited to,nickel, copper, iron, tin, zinc, ruthenium, palladium, rhenium, or anyof the other transition or lanthanide metals, or a noble metal such asplatinum, palladium, gold, or silver. They may also include productsthereof, including for example cuprous chloride or cuprous oxide, othercompounds of catalytic metals, as well as organometalic compounds.Exemplary organometallie compounds include, but are not limited to,tetraearhonyl nickel, lithiumdiphenylcuprate, pentamesitylpentacopper,and etharatedimer.

The electrolyte 120 will also be implementation specific depending, atleast in part, on the implementation of the reaction electrode 116.Exemplary liquid ionic substances include, but are not limited to,Alkali or alkaline Earth salts, such as halides, sulfates, sulfites,carbonates, nitrates, or nitrites. The electrolyte 120 may therefore be,depending upon the embodiment, magnesium sulfate (MgS), sodium chloride(NaCl), sulfuric acid (H₂SO₄), potassium chloride (KCl), hydrogenchloride (HCl), hydrogen bromide (HBr), hydrogen fluoride (HF),potassium chloride (KCl), potassium bromide (KBr), and potassium iodide(KI), or any other suitable electrolyte and acid or base known to theart.

The pH of the electrolyte 120 may range from 0 to 3 and concentrationsof between 0.1 M and 3 M may be used. Some embodiments may use water tocontrol pH and concentration, and such water may be industrial gradewater, brine, sea water, or even tap water. The liquid ion source, orelectrolyte 120, may comprise essentially any liquid ionic substance. Insome embodiments, the electrolyte 120 is a halide to benefit catalystlifetime.

In addition to the reactor 105, the electrochemical cell 100 includes agas source 145 and a power source 150, and an electrolyte source 163.The gas source 145 provides the gaseous methane feedstock 130 while thepower source 150 is powering the electrodes 115, 116 under enoughpressure to balance and overcome the gravitational pressure of thecolumn of electrolyte, which depends on the height of the water,sufficient to maintain the reaction at the three phase interface 155.The three phase interface 155 defines a reaction area. In someembodiments, this pressure might be, for example, 10000 pascals, or from0.1 ATM to 10 ATM, or from 0.1 ATM to 100 ATM. The electrolyte source163 provides adequate levels of the electrolyte 120 to ensure properoperations. The three phases at the interface 155 are the liquidelectrolyte 120, the solid catalyst of the reaction electrode 116, andthe gaseous methane feedstock 130. The product 160 is collected in avessel 165 of some kind in any suitable manner known to the art.

The embodiment of FIG. 1 includes only a single reactor 105. However, inalternative embodiments, multiple units of these may be arranged forgreater efficiencies. In a larger single chamber, pressure would morelikely have to be adjusted with electrolyte level rather than changes ingaseous methane feedstock 130 pressure in the chamber 125.

Those in the art will appreciate that some implementation specificdetails are omitted from FIG. 1. For example, various instrumentationsuch as flow regulators, mass regulators, a pH regulator, and sensorsfor temperatures and pressures are not shown but will typically be foundin most embodiments. Such instrumentation is used in conventionalfashion to achieve, monitor, and maintain various operational parametersof the process. Exemplary operational parameters include, but are notlimited to, pressures, temperatures, pH, and the like that will becomeapparent to those skilled in the art. However, this type of detail isomitted from the present disclosure because it is routine andconventional so as not to obscure the subject matter claimed below.

The reaction is conceptually illustrated in FIG. 2. In this embodiment,the feedstock 130′ is natural gas and the electrolyte 120′is SodiumChloride. Reactive hydrogen tons (H⁺) are fed to the natural gas stream130′ through the electrolyte 120′ with an applied cathode potential. Themolecules may also in turn react with water on the interface to formalcohols, oxygenates, and ketones. Exemplary alcohols include but arenot limited to methanol, ethanol, propanol, butanol. In one example ofthis reaction, the reaction occurs at room temperature and with anapplied cathode potential of 0.01 V versus SHE to 1.99V versus SHE. Thevoltage level can be used to control the resulting product. A voltage of0.1V may result in a methanol product whereas a 0.5V voltage may resultin butanol.

Still further, very little catalyst deactivation occurs in someembodiments because the catalyst is protected by a layer of chloride,which also acts as an absorbent for the reactants, and the electrolyteis saturated with Cl⁻ preventing typical catalyst poisons from bondingwith the catalyst and deactivating it, as this would force the releaseof a Cl⁻ion into the liquid. In addition, this process further preventsthe deposition of impurities in water, which could deactivate thecatalyst. These aspects will be explored further below.

Returning now to FIG. 1, additional attention will now be directed tothe electrochemical cell 100. As noted above, the reactor 105 can befabricated from conventional materials using conventional fabricationtechniques. Notably, the presently disclosed technique operates at roomtemperatures and pressures whereas conventional processes are performedat temperatures and pressures much higher. Design considerationspertaining to temperature and pressure therefore can be relaxed relativeto conventional practice. However, conventional reactor designs maynevertheless be used in some embodiments.

The presently disclosed technique admits variation in the implementationof the electrode at which the reaction occurs, hereafter referred to asthe “reaction electrode”. The other electrode will be referred to as the“counter electrode”. In the embodiment of FIG. 1 the reaction electrode116 is the reaction electrode and the counter electrode 115 is thecounter electrode. As noted above, those in the art will appreciate thatthe identity of the electrodes 115, 116 as cathode and anode is a matterof polarity that can vary by implementation.

One such modification is that the copper mesh used in the illustratedembodiment is an 80 mesh rather than a 40 mesh. This mesh may be platedwith high current densities to produce fractal foam structures with highsurface areas which may be utilized as catalysts in this reaction.

More particularly, the catalyst 305 is supported on a copper mesh 310embedded In an ion exchange resin 300 as shown in FIG. 3A. The catalyst305 can be a plated catalyst or powdered catalyst. The metal catalyst305 is a catalyst capable of reducing methane to a long chainedhydrocarbon or organic compound and alcohol Exemplary metals include,but are not limited to, metals such as copper, silver, gold, iron, tin,zinc, ruthenium, platinum, palladium, rhenium, or any of the othertransition or lanthanide metals. In one embodiment, the metal catalystis silver, copper, copper chloride or copper oxide. Ion exchange resinsare well known in the art and any suitable ion exchange resin known tothe art may be used. In one particular embodiment, the ion exchangeresin is NAFION 117 by Dupont

The copper wire mesh 310 can be used to structure the catalyst 305within the resin 300. The assembly 315 containing the catalyst 305 canbe deposited onto or otherwise structurally associated with ahydrophilic paper 320, as shown in FIG. 3B. Electrical leads (not shown)can then be attached to the copper wire mesh 310 in conventionalfashion. The reaction electrode 320 is but one implementation of thereaction electrode 116 in FIG. 1. Alternative implementations will bediscussed below.

The counter electrode 115, the reaction electrode 116 is disposed withina reactor 105 so that, in use, it is submerged in the electrolyte 120and the catalyst 305 forms one part of the three-phase interface 155.When electricity is applied to electrodes 115, 116, electrochemicalreduction discussed above takes place to produce hydrocarbons andorganic chemicals. The reaction electrode 320 receives the electricalpower and catalyzes a reaction between the hydrogen in the electrolyte120 and the gaseous methane feedstock 130.

As mentioned above, the copper mesh 310 in the illustrated embodiment isan mesh in the range of 1-400 mesh.

In a second embodiment shown in FIG. 4A-FIG. 4B, a gas diffusionelectrode 400 comprises a hydrophobic layer 405 that is porous tomethane but impermeable or nearly impermeable to aqueous electrolytes.In one embodiment of the electrode 400, a 1 mil thick advcarb carbonpaper 410 treated with TEFLON® (i.e., polytetrafluoroethylene)dispersion (not separately shown) is coated with activated carbon 415with copper 420 deposited in the pores of the activated carbon 415. Thecopper 420 may be deposited through a wet impregnation method,electrolytic reduction, or other means of reduction of copper, silverother transition metals into the porous carbon material.

This material is then mixed with a hydrophilic binding agent (notshown), such as polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), orNafion. An ink is made from the mixture of impregnated graphite, bindingagent, and alcohol or other organic solvent. The ink is painted onto thehydrophobic layer 405 and then bonded through any means, such asatmospheric drying, heat press, or other means of application of heat.

The copper 420 impregnated into the ion electrode 400 is then made intoa cuprous halide through any suitable procedure. One embodiment of theprocedure to make the cuprous halide is to submerge the electrode in asolution of hydrochloric acid and cupric chloride, heat to 100° C. for 2hours. Another embodiment submerges the impregnated electrode 400 in 3 MKBr or 3 M KI and run a 4 V pulse of electricity to the electrode 400 inorder to form a thin film of cuprous halide 425, shown in cross-sectionFIG. 4B, in the electrode 400.

In another embodiment, the copper particles in the electrode are firstplated with silver by electroless plating or another method, creating athin film of silver over the copper. Copper may then be plated onto thesilver and transformed into a halide through procedure previouslydescribed. In another embodiment, silver particles are deposited intothe hydrophilic layer, coated with copper electrolytically, and then thesame procedure for the conversion of the copper layer to a copper halidelayer is conducted.

In another embodiment, the gas diffusion electrode uses nanoparticlesreduced from a solution of Cupric Chloride with an excess of ascorbicacid and 10 grams of carbon graphite. The amalgam was heated to 100° C.for eight hours. It is then mixed with equal amounts in weight of ahydrophilic binder.

In another embodiment, a high mesh copper of 200 mesh is allowed to formcuprous chloride in a solution of cupric chloride and hydrochloric acid.This layer of halide on the surface of the catalyst material allows forcatalyst regeneration. This accounts for the abnormally high lifetime ofthe three phase reaction. The result is then treated in a 1 M solutionof Cupric Chloride heated to 100° C.

The electrode 400 therefore includes a covering or coating 425 ofcuprous chloride to prevent “poisoning” or fouling of the electrode 400during operation. The electrodes in this embodiment must be copper sothat no other metals foul the reaction by creating intermediate productswhich ruin the efficacy of the surface of the copper. Some embodimentsalso treat the copper with a high surface area powder by electroplating,which will allow for the generation of greater microturbulence, therebycreating more contact and release between the three phase reactionsurface. Furthermore, contrary to conventional practice, rather thanseparate the cathode and anode, the cathode and anode are allowed toremain in the same electrolyte in this embodiment. (The electrolyte isfiltered through a pump not shown.) The electrolyte is thereforecontacted directly to the gas diffusion electrode 400 rather thanthrough the intercession of a polymer exchange membrane.

Catalysts in this particular embodiment may include copper, silver,gold, iron, tin, zinc, ruthenium, platinum, palladium, rhenium, or anyof the other transition or lanthanide metals. In addition, the catalystsmay be formed into a metal foam or alternatively it may be depositedthrough electroless or electrolytic deposition onto a porous supportwith a hydrophobic and hydrophilic layer.

In electrochemical systems, it is often difficult to make a goodelectrical contact between gas diffusion medium and the currentcollector. The need for a solid polymer electrolyte to some degree isthe first order solution to the problem at hand. Carbon paper has asignificant resistance across of up to 2Ω that impedes the effectiveapplication of gas diffusion electrodes to electrochemical applications.By pressing a wire made from a metal such as nickel, copper, iron,steel, or a noble metal such as platinum, gold, or silver directly intothe carbon paper, gas diffusion media may be extended into applicationssuch as hydrocarbon processing and fuel cell applications. Theproduction of such papers is relatively straight forward though requiresa few enabling aspects for it to work. A small amount of adhesivematerial is mixed in with activated carbon particles with a highinternal porosity, for example a BET of 50 m²/gram. This serves as thebinder which may be applied between existing conductive gas diffusionmedium such as a carbon paper, a toray paper, or other conductive gasdiffusion electrodes. FIG. 5A shows one embodiment 500 of the pressedwire mesh 505 in paper 510. The wire 505 is first submerged in a slurryof activated carbon and adhesive (not shown), which is mixed in a ratioby weight of 1:1 that provides for full conductivity of the thin bindinglayer. This layer than presses the wire mesh 505 into the surface of thecarbon paper 510, providing uniform conductivity.

The binder slurry both binds the metal of the wire mesh 505 to thesurface of the conductive paper 510, while providing conductivity itselfand holds the wire mesh 505 firm against the conductive paper 510, whichovercomes the contact resistance. The surface of the wire mesh 505 iscleaned with a solvent before being applied to the carbon paper 510 toremove any oils from the surface of the contact region, as this maycause unwanted resistance to build up. The wire should be thick enoughthat the wire mesh 505 forms a slight indentation into the paper 510 asto provide maximum contact area.

In another embodiment 500′, the production of the paper 510 is conductedand deposited directly onto the wire mesh 505, the result of which isshown in FIG. 5B. Conductive carbon paper is often made by pyrolyzingcarbon containing compounds. Thus, by using a conductive material withhigh corrosion resistance in a low oxygen environment, it would bepossible to convert carbon containing material directly onto the wiremesh conductor, providing for a single step process to deposit. Theprocess may otherwise be in accordance with conventional practice forproducing and pyrolyzing carbon based materials to form carbon papersuch as polyanaline based carbon fiber paper.

The technique illustrated in FIG. 5A-FIG. 5B can improve theconductivity of the carbon papers 510 and significantly reduce theresistance thereof by up to an ohm or more. In the embodiment 500 ofFIG. 5A, more particularly, a carbon paper 510 has a 1-400 mesh purecopper mesh 505 embedded halfway into the carbon paper 510. In theembodiment 500′ of FIG. 5B, the carbon paper 510 has the copper wiremesh 505 embedded in therein such that no metal is showing. Spacingbetween the wires of the mesh 505 can be from 1 mm to 1 cm. The carbonpaper 510 should generally be as thin as possible while still beingsturdy enough to withstand handling in both embodiments.

In one particular embodiment, the electrodes are electrically shortcircuited within the electrolyte while maintaining a three phaseinterface. FIG. 6 depicts a portion 600 of an embodiment in which theelectrodes are electrically short circuited. In this drawing, only asingle electrode 605 is shown but the potential is electric potential isdrawn across the electrode 605. The companion electrode (not shown) issimilarly electrically short circuited.

So, turning now to the process again and referring to FIG. 1, a methanegas or gaseous mixture including methane 130 is introduced into thesecond chamber 125 of the reactor 105 under pressure. The exemplaryembodiments discussed below all include the following designcharacteristics: (1) a three-phase catalytic interface 155 for solidcatalyst, gaseous methane feedstock 130, and liquid ion source (e.g., aliquid electrolyte) 120, (2) a cathode 116 and anode 115 in the same,filtered electrolyte 120, and (3) an electrolyte 120 contacted directlyto the reaction electrode, which is the cathode 116.

The method of operation generally comprises introducing the electrolyte120 into the first chamber 110 into direct contact with the poweredelectrode surfaces 115 and 116. The gaseous methane feedstock 130 isthen introduced into the second chamber 125 under enough pressure toover come the gravitational pressure of the column of electrolyte, whichdepends on the height of the water, to induce the reaction. During thereaction, the electrolyte 120 is filtered, the gaseous methane feedstock130 is maintained at a selected pressure to ensure its presence at thethree phase interface 155, and the product 165 is collected. Within thisgeneral context, the following examples are implemented.

Above the second chamber 125, but attached to it, is an area for theintroduction of a cathode reaction electrode 116 where the three-phaseinterface 155 will form. Catalysts supported by the reaction electrode116 include copper, silver, gold, iron, tin, zinc, ruthenium, platinum,palladium, rhenium, or any of the other transition or lanthanide metals.In addition, the catalysts may be formed into a metal foam oralternatively it may be deposited through electroless or electryticdeposition onto a porous support with a hydrophobic and hydrophiliclayer as previously described above. The electrolyte 120 may comprise,for example, potassium chloride (KCl), potassium bromide (KBr),potassium iodide (KI), or any other suitable electrolyte known to theart.

This particular embodiment implements the reaction electrode 116 as thegas diffusion electrode described above with the cuprous halide coating.Alternative embodiments may use another cuprous halide coating thesurface of the metal. Cuprous Oxide, Cupric Oxide, and other varyingvalence states of copper will also work in the reaction.

By maintaining a three phase interface between gaseous methane feedstock130 and the electrolyte 120, the methane will form organic chemicals andform a nearly complete conversion when there is continuous contact tothe gaseous methane feedstock 130 on the three phase interface 155between the liquid electrolyte 120, the solid catalyst, and the gaseousmethane feedstock 130. Another means of maintaining the three phaseinterface is to use a separation membrane which selectively allowshydrogen and water to penetrate. One such membrane is Nafion. Anothermeans is to use a fuel cell type set up but instead of generating acurrent, a current is introduced to generate a chemical.

Other reaction mechanism also produces organic compounds such as ethers,epoxides, and alcohols, among other compounds.

The electrolyte 120 should be relatively concentrated at 0.1 M-3 M andshould be a halide electrolytes discussed above to increase catalystlifetime. The higher the surface area between the reaction electrode 116and the gaseous chamber 125 on one side and the liquid electrolyte 120on the other side, the higher the conversion rates. Operating pressurescould be ranged from only 10000 pascals, or from 0.1 atm to 100 atm, orfrom 0.1 atm to 100 atm, though Standard Temperature and Pressures (STP)were sufficient for the reaction.

In one embodiment of the gas diffusion electrode (GDE) an antioxidantlayer of ascorbic acid is mixed with the GDE high porosity carbon. Thehigh porosity carbon includes nanotubes, fullerines, and otherspecialized formations of carbon as described above. The high porositycarbon is impregnated through reduction of cupric chloride, or otherform of carbon. It is then made into a halide by treatment with achloride solution under the proper pH and temperature of EMF conditions.It also includes a reaction in the solid polymer phase. A paste is madefrom the impregnated carbon, ascorbic acid, and a hydrophilic bindingagent. This paste is painted onto a hydrophobic layer. Some embodimentsinclude antioxidants in the layer as described above.

Note that not all embodiments will manifest ail these characteristicsand, to the extent they do, they will not necessarily manifest them tothe same extent. Thus, some embodiments may omit one or more of thesecharacteristics entirely. Furthermore, some embodiments may exhibitother characteristics in addition to, or in lieu of, those describedherein.

The phrase “capable of” as used herein is a recognition of the fact thatsome functions described for the various parts of the disclosedapparatus are performed only when the apparatus is powered and/or inoperation. Those in the art having the benefit of this disclosure willappreciate that the embodiments illustrated herein include a number ofelectronic or electro-mechanical parts that, to operate, requireelectrical power. Even when provided with power, some functionsdescribed herein only occur when in operation. Thus, at times, someembodiments of the apparatus of the invention are “capable of”performing the recited functions even when they are not actuallyperforming them—i.e., when there is no power or when they are poweredbut not in operation.

The following patent, applications, and publications are herebyincorporated by reference for all purposes as if set forth verbatimherein:

U.S. Application Ser. No. 61/608,583, entitled, “An ElectrochemicalProcess for Direct one step conversion of methane to Ethylene on a ThreePhase Gas, Liquid, Solid Interface,” and filed Mar. 8, 2012, in the nameof the inventor Ed Chen and commonly assigned herewith.

U.S. Application Ser. No. 61/713,487, entitled, “A Process forElectrochemical Fischer Trospch,” filed Oct. 13, 2012, in the name ofthe inventor Ed Chen and commonly assigned herewith.

To the extent that any patent, patent application, or other referenceincorporated herein by reference conflicts with the present disclosureset forth herein, the present disclosure controls.

This concludes the detailed description. The particular embodimentsdisclosed above are illustrative only, as the invention may be modifiedand practiced in different but equivalent manners apparent to thoseskilled in the art having the benefit of the teachings herein.Furthermore, no limitations are intended to the details of constructionor design herein shown, other than as described in the claims below. Itis therefore evident that the particular embodiments disclosed above maybe altered or modified and all such variations are considered within thescope and spirit of the invention. Accordingly, the protection soughtherein is as set forth in the claims below.

What is claimed:
 1. A method for chain modification of hydrocarbons andorganic compounds comprising: contacting an aqueous electrolyte, apowered electrode including a catalyst, and a gaseous methane feedstockin a reaction area; and activating the methane in an aqueouselectrochemical reaction to generate methyl radicals at the poweredelectrode to yield a product.
 2. The method of claim 1, wherein gaseousmethane feedstock is a methane stream or natural gas.
 3. The method ofclaim 1, wherein the product includes long chained hydrocarbons.
 4. Themethod of claim 3, wherein the product includes ethylene, butane, oroctane.
 5. The method of claim 3, wherein the product further includesmethanol and higher alcohols.
 6. The method of claim 1, wherein theproduct includes alcohols.
 7. The method of claim 6, wherein thealcohols include methanol, ethanol, propanol, butanol.
 8. The method ofclaim 1, wherein the catalyst comprises a metal, an inorganic salt of ametal, or an organometallic compound.
 9. The method of claim 6, whereinthe aqueous electrolyte includes Alkali or Alkaline Earth Salts.
 10. Amethod for chain modification of hydrocarbons and organic compoundscomprising: contacting an aqueous electrolyte with a catalyst in areaction area; introducing a gaseous methane feedstock directly into thereaction area; and reacting the aqueous electrolyte, the catalyst, andthe gaseous methane feedstock at temperatures in the range of −10 C to1000 C and at pressures in the range of 0.1 ATM to 100 ATM.
 11. Themethod of claim 10, wherein gaseous methane feedstock is a methanestream or natural gas.
 12. The method of claim 10, wherein reacting theaqueous electrolyte, the catalyst, and the gaseous methane feedstockincludes powering the reaction electrodes.
 13. The method of claim 10,wherein reacting the aqueous electrolyte, the catalyst, and the gaseousmethane feedstock includes shorting out the reaction electrodes withinthe electrolyte while maintaining a three phase interface.
 14. Themethod of claim 10, wherein introducing the aqueous electrolyte intocontact with the reaction electrode includes introducing the aqueouselectrolyte into direct contact with a gas diffusion electrode.
 15. Themethod of claim 10, wherein introducing the aqueous electrolyte intocontact with the reaction electrode includes introducing liquidreactants into direct contact with a gas diffusion electrode.
 16. Themethod of claim 10, wherein: the supported catalyst is a solid; and thereaction occurs at a three-phase interface between the aqueouselectrolyte, the solid catalyst, and the gaseous methane feedstock. 17.The method of claim 10, further comprising leaving the aqueouselectrolyte unfiltered during the reaction.
 18. The method of claim 8,wherein the catalyst comprises a metal, an inorganic salt of a metal, oran organometallic compound.
 19. The method of claim 18, wherein thecatalyst contains an element selected from the group comprising copper,silver, gold, nickel, iron, tin, zinc, ruthenium, platinum, palladium,rhenium, and a lanthanide metal.
 20. The method of claim 18, wherein thecatalyst contains an organometallic salt of an element selected from thegroup comprising copper, silver, gold, nickel, iron, tin, zinc,ruthenium, platinum, palladium, rhenium, and a lanthanide metal.
 21. Themethod of claim 18, wherein the catalyst is Cuprous Chloride or CuprousOxide.
 22. The method of claim 18, wherein the aqueous electrolyteincludes Alkali or Alkaline Earth Salts.
 23. The method of claim 22,wherein the Alkali or alkaline Earth Salts include Halides, Sulfates,sulfites, Carbonates, Nitrates or Nitrites.
 24. The method of claim 22,wherein the aqueous electrolyte is selected from the group comprisingmagnesium sulfate, sodium chloride, sulfuric acid, potassium chloride,hydrogen chloride), potassium chloride, potassium bromide, potassiumiodide, sea salt, and brine.
 25. The method of claim 8, wherein theaqueous electrolyte is selected from the group comprising magnesiumsulfate, sodium chloride, sulfuric acid, potassium chloride, hydrogenchloride), potassium chloride, potassium bromide, potassium iodide, seasalt, and brine.
 26. The method of claim 8, wherein the aqueouselectrolyte has a concentration of between 0.1 M-3 M.
 27. The method ofclaim 8, wherein the reaction electrode is a gas diffusion electrode.28. The method of claim 25, wherein the gas diffusion electrode iscoated with a copper containing salt.
 29. The method of claim 8, whereinthe product includes long chained hydrocarbons.
 30. The method of claim29, wherein the product includes ethylene.
 31. The method of claim 29,wherein the product further includes methanol and higher alcohols. 32.The method of claim 8, wherein the product includes alcohols.
 33. Themethod of claim 32, wherein the alcohols include methanol, ethanol,propanol, butanol